Controlling polymerization of polyhydric alcohol esters of alphaolefinic dicarboxylic acids with ethylenic monomers



Patented Sept. 14, 1948 CONTROLLING POLYMERIZATION F POLY- HYDRIC ALCOHOL ESTERS 0F ALPHA- OLEFINIC DICARBOXYLIC ACIDS WITH ETHYLENIC MONOMERS Everett 0. Hui-dis, Passaic, N. J., assignor to United States Rubber Company, New York, N. Y., a corporation of New Jersey No" Drawing. Application December 30, 1944.

Serial No. 570,766

Claims. (Cl. 260-454) This invention relates to improvements in the manufacture or products, and fabricated articles, from certain resins oi the general class known as non-by-product-iorming polymerizable resins. These resins are formed 0! liquid or semi-liquid polymerizable components which polymerize together, or interpolymerize, in what is known as the oil phase, without splitting ofi by-proclucts, e. g., water, to form, eventually, hard resins. Usually, this reaction is expedited by the use of an oxygen-containing polymerization catalyst such as benzoyl peroxide, peroxides of aliphatic acids, ascaridole, and other organic peroxides, but even so temperatures of 50 C. to 125 C. are usually required for rapid gelation and polymerization.

It is the purpose of this invention to provide a practical means for greatly accelerating at temperatures below 50 C. the interpolymerization of unsaturated alkyd resins with monoenlc compounds having a single" terminal ethylenic group CH2=C It is, as stated, customary to carry out such polymerizations at temperatures between 50 C. and 125 C., using as catalysts such oxygen containing compounds as benzoyl peroxide, peroxides of aliphatic acids, ascaridole, and other organic peroxides. The speed with which these known systems polymerize can be regulated within certain limits by regulating the amount of catalyst added and the temperature at which polymerization is carried out. It is possible by such means to prepare systems which will polymerize in a few minutes at the higher temperature, 1. e., about 50 C. It is also customary to add polymerization inhibitors such as benzaldehyde, para-tertiary-butylcatechol, hydroquinone, tetrochloroquinone, and phenyl-enaphthylamine to the liquid polymerizable systems to prevent premature polymerization during storage. This desired storage stability is of necessity accompanied by a decrease in the overall rate at which polymerization takes place in the presence of the usual catalysts such as benzoyl peroxide. Thus, with such stabilized polymerizable systems, it becomes necessary to use more catalyst to obtain a, given rate of polymerization than would be necessary with an uninhibited polymerizable system.

Although it is of course possible to accelerate the polymerization of certain systems containing no added inhibitor so that they will polymerize at temperatures below 50 C. in periods 01 time ranging from a few hours to several days, such an increase in polymerization speed means the sacrifice of the storage stability of the uncatalyzed polymerizable system. Such uninhibited systems often tend to polymerize spontaneously on standing and to become unstable. Hence, this method of increasing the rateoi polymerization at temperatures below 50 C. is impractical.

An object oithe invention is to provide certain chemical means (called herein promoters) adjunctive to said oxygen-containing catalyst, for promoting the gelation and thereby increasing the overall rate of polymerization at temperatures below 50 C., and thereby giving to the liquid resinous mix cold-setting and cold-curing properties. It will be at once apparent that this permits new and improved fabricating techniques and speeding up of production. Of particular adaptability to this technique is the class of resins produced from polymerizable mixtures of unsaturated alkyd resins with monoenic com- 'pounds, to which belong the resins represented by the polyethylene glycol maleate-styrene copolymer resins covered by the Ellis U. S. Patents Nos. 2,255,313 and 2,195,362 and the American Cyanamid Co. British Patents Nos. 540,167 and 540,168. These resins harden to form tough, noncracking surfaces.

I have found that by using in conjunction with a conventional catalyst, such as benzoyl peroxide, a small amount of an N-mono-alkyl mono(monocyclic-aryl) secondary monoamine, I can greatly increase the overall rate of p lymerization at temperatures below 50 C. of polymerizable mixtures of unsaturated alkyd resins with monoenic compounds having a single terminal ethylenic group CH2=C Small quantities of these N- monoalkyl mono(monocyclic-aryl) secondary monoamines are effective in increasing the overall speed of polymerization of such polymerizable mixtures containing polymerization inhibitors at temperatures below 50 C. to such an extent that these systems may be polymerized in a few minutes. This rapid rate of polymerization is gained without any accompanying sacrifice of the storage stability of the polymerizable systems. Rapid polymerizations at low temperatures are thus made completely practical.

The responsiveness to the present invention of the herein described polymerizable mixtures of unsaturated alkyd resins with monoenic compounds having a single terminal ethylenic group CH2=C seems to reside in their property of being capable oi. polymerizing relatively rapidly in the presence of peroxide catalyst and in the absence 01! any added promoter, compared with other members of the general class of non-byproduct-forming polymerizable resins.

Polymerizable systems of the type to which my invention is applicable are commonly used in the fabrication of laminated articles composed of absorptive or porous sheet materials such as by known methods so that it has the proper vis- The impregnated sheet materials may then be plied together and formed to the desired shape.

Heat is then applied to raise the temperature of the polymerizable mixture to a point where the polymerization will take place at a rapid enough rate. This temperature is usually well above 50 C. and usually in the neighborhood of 125 C. While it is necessary to raise the temperature to speed up the polymerization of the mixture, this increase in temperature brings about an undesirable decrease in the viscosity of the liquid mixture, with the result that the liquid tends to flow away from spaces between the layers of fabric and paper, leaving so-called starved spots or areas where there will be insufilcient polymer in the finished articles. This is also true with vertical areas. 'Difiiculty has been encountered in forming smooth surfaces on fiat sheets with such resins.

On the other hand, by using a polymerizable mixture containing a catalyst and a sufiicient amount of a monoalkyl-monophenyl secondary monoamine to cause rapid polymerization at temperatures below about 50 C., it is not necessary to raise the temperature above 50 C. in order to cause the mixture to set to a non-fiowable state. Low viscosity effects are thus avoided. It is thus possible to allow the mixture to set or gel at room temperature or slightly above and then, if desired, to complete the polymerization at an elevated temperature without causing unequal distribution of the resin (formation of starved areas) since no decrease in viscosity will take place.

Although the principles of my invention are particularly useful in the production of laminated articles they can also be satisfactorily applied to the production of castings or coatings whereever it is desired to have rapid polymerization at low temperatures.

The polymerization of the systems involved in this invention takes place in several recognizable stages. The resin mixture remains quite fluid with little or no change in viscosity during a period of time called the induction period. After this the viscosity increases very rapidly until the mixture becomes a soft solid. The time necessary to reach this stage is called the gel time. The material, if undisturbed, continues to increase in hardness gradually until a hard solid stage is reached.

In carrying out polymerizations in the oil phase according to this invention, several procedures may be followed. It is preferred to dissolve the peroxide catalyst in the less viscous of the resin components, which is then mixed with the other resin component. The promoter may then be incorporated directly in the mixture, which is then ready for use in casting or for producing such articles as are desired. (It has not been found practical to add the promoter to either of the resin components at a time long before use since the activity of the promoter is gradually destroyed on standing.)

If a casting is to be made, the mixture is poured into a previously prepared form and allowed to stand at temperatures ranging from to 50 C. until the resin has polymerized at least to the gel point. If the resin is to be used for impregnating or coatings, it is applied to the desired base material which may either be shaped immediately and the gel allowed to form in a horizontal position after which the article can be molded and the .rest of the polymerization ."carried out at a higher temperature.

4 to at least one negative radical.

The base materials subject to impregnating or coating may be in sheet, filament, or other form, and comprise materials of metal, vegetable, animal, mineral, orsynthetic nature. The monoenic compounds used in the invention are those which are capable of addition polymerization and contain one and only one terminal CH2 group doubly bonded to a carbon atom which in turn is bonded Specific examples of such compounds are: styrene. in which the negative group is the phenyl radical: vinyl chloride, in which it is the chloride radical; vinyl acetate, in which it is the acotoxy radical; esters of acrylic and methacrylic acids, in which it is a carbo-ester radical: acrylonitrile and methacrylonitrile, in which it is the carbonitrile radical.

The unsaturated alkyds used in the invention are prepared in known manner by the reaction of a polyhydric alcohol with unsaturated dicarboxylic acids or their anhydrides with or without the presence of modifying agents, such as monohydric alcohols, saturated monocarboxylic acids, saturated polycarboxylic acids, drying or semi-drying oils, etc. Unsaturated alkyds of this type are described, for example, in U. S. Patents Nos. 2,195,362 and 2,255,313.

The unsaturated organic acids which I prefer in preparing the aikyds used in the invention are maleic, fumaric, citraconic, itaconic, mesaconic, aconitic, chioromaleic, and carbic acids. The polyhydric alcohols preferred for use in the invention are ethylene glycol, diethylene glycol, triethyiene glycol, other polyethylene glycols, propylene glycol, 2,2-dimethyl-propanediol-1,3, glycerol, pentaerythritol, 1,3-butanediol, polymethylene glycols (e. g., trimethylene glycol), and 2- ethyl-2-butylbutanediol- 1,3.

The proportions in which the interpolymerizable components are mixed may be varied widely;

' e. g., the amount of the polyenic alkyd may range range for the promoter ranges from 0.005 to 2.0'

parts per parts by weight of the polymerizable mixture.

The following examples are given further to illustrate the invention, the parts being by weight:

EXAMPLE I A reactive alkyd is prepared by reacting 1.05 mols of diethylene glycol with 1.00 mol of maleic anhydride at C. in a carbon dioxide at mosphere until an acid number of 50 is attained.

Two parts of benzoyl peroxide are dissolved in 30 parts of monomeric styrene containing 0.010 part of p-tertiary-butyl-catechol (inhibitor). Seventy parts of the alkyd are then dissolved For any given system of in-.

in the styrene solution by stirring. As soon as this mixture is homogeneous, 0.2 part of N-ethylm-toluidine is added and the mixture stirred for one minute. In Table I are noted the comparative times in which gelation occurs for the above mixture, for a mixture to which benzoyl peroxide but no amine is added, and for ,a mixture to which neither amine nor catalyst has been added.

This example illustrates clearly the tremendous effect obtained by the use of the combination of monoaryl-monoalkyl secondary monoamine with the peroxide catalyst in the inhibited resincombination.

EXAMPLE II Table II lists the gelling times which were observed with various monoalkyl monophenyl secondary amine promoters used in accordance with the invention. The amount of promoter indicated in the table was added to the resin combination consisting of 70 parts of a reactive alkyd produced by the method of Example 1, 30 parts of monomeric styrene, 0.01 part of p-tertiarybutylcatechol and one part of benzoyl peroxide in the manner described above.

It may be seen from this table that a small amount of a monoalkyl mcnophenyl secondary amine produces a tremendous effect when used in conjunction with benzoyl peroxide catalyst.

Table II Concentra- Gel time Promoter g g (min. at

resin) 25 C.)

N-methylaniline Although I have shown and described various embodiments of this invention, it is to be understood that the invention is susceptible to those modifications which appear within the spirit of the invention and the scope of the claims.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. In a method of controlling the oil phase gelling and polymerization of a polymerizable mix comprising a liquid polyhydric alcohol ester of an alpha-olefinic dicarboxylic acid, and a liquid monomeric unsaturated polymerizable compound in which the unsaturation is due to a single terminal ethylenic group which is attached to a negative radical, and in which the said ester is soluble and with which ester it is copolymerizable in the presence of a peroxy polymerization catalyst, said catalyst also being present, that improvement which consists in the step of adding a small but effective amount of a promoter of gelation which is a secondary monoamine that contains attached to the nitrogen atom one functionally aliphatic radical selected from the class consisting of alkyl hydrocarbons having from 1 to 5 carbon atoms and beta-hydroxyethyl, and one aromatic hydrocarbon radical of the benzene series.

2. In a method of controlling the oil phase gelling and polymerization of a polymerizable mix comprising a liquid polyhydric alcohol ester of an valpha-oleiinic dicarboxylic acid, and a liquid monomeric unsaturated polymerizable compound in which the unsaturation is due to a single terminal ethylenic group which is attached to a negative radical, and in which the said ester is soluble and with which ester it is copolymerizable in the presence of a peroxy polymerization catalyst, said catalyst also being present, that improvement which consists in the step of addin a small but effective amount of a promoter of gelation which is N-methylaniline.

3. In a method of controlling the oil phase gelling and polymerization of a polymerizable mix comprising a liquid polyhydric alcohol ester of an aipha-olefinic dicarboxylic acid, and a liquid monomeric unsaturated polymerizable compound in which the unsaturation is due to a single terminal ethylenic group which is attached to a negative radical, and in which the said ester is soluble and with which ester it is copolymerizable in the presence of a peroxy polymerization catalyst, said catalyst also being present, that improvement which consists in the step of adding a small but effective amount of a promoter of gelation which is N-isoamylaniline.

4. In a method of controlling the oil phase gelling and polymerization of a polymerizable mix comprising a liquid polyhydric alcohol ester of an alpha-olefinic dicarboxylic acid, and a liquid monomeric unsaturated polymerizable compound inwhich the unsaturation is clue to a. single terminal ethylenic group which is attached to a negative radical, and in which the said ester is soluble and with which ester it is copolymerizable in the presence of a peroxy polymerization catalyst, said catalyst also being present, that improvement which consists in the step of adding a small but eiiective amount of a promoter of gelation which is N -ethylaniline.

5. A polymerizable mixture comprising a liquid polyhydric alcohol ester of an alpha-oleiinic dicarhoxylic acid, and a liquid monomeric unsaturated polymerizable compound in which the unsaturation is due to a single terminal ethylenic group which is attached to a negative radical, and in which the said ester is soluble and with which ester it is copolymerizable in the presence of a peroxy polymerization catalyst, said catalyst also being present, and in addition a small but effective amount of a promoter of gelation which is a secondary monoamine that contains attached to the nitrogen atom one functionally aliphatic radical selected from the class consisting of alkyl hydrocarbons having from 1 to 5 carbon atoms and beta-hydroxyetnyl, and one aromatic hydrocarbon radical of the benzene series.

EVERETT C. HURDIS. 

